The present invention relates to novel trifluorobutenes, processes for their preparation and their use as a nematicidal agent.
Japanese Laid-open Patent Publication No. 85267/1990 describes substituted azolethioethers which have insecticidal activity. U.S. Pat. No. 3,513,172 describes that some kinds of trifluorobutenyl compounds have nematicidal activity and Japanese Laid-open Patent Publication (PCT) No. 500037/1988 describes that some kinds of polyhaloalkene compounds have nematicidal activities. Further, WO 95/24403 describes that 4,4-difluorobutenyl compounds have nematicidal activity.
There have now been found novel trifluorobutenes of formula (I) 
wherein
R1 represents hydrogen, halogen, or alkyl which may be unsubstituted or substituted with halogen, hydroxy, alkoxy, alkylthio, alkylcarbonyloxy, haloalkylcarbonyloxy or cyano, or represents alkylsulfonyloxy or represents phenyl which may be unsubstituted or substituted with halogen, alkyl, haloalkyl, alkoxy, alkylthio, alkylsulfonyl, haloalkoxy, haloalkylthio, phenyl, phenoxy, cyano or nitro.
R2 represents hydrogen, halogen, or alkyl which may be unsubstituted or substituted with alkoxy or halogen, or represents alkoxycarbonyl, and
n represents 0, 1 or 2.
provided that if R1 represents alkyl, R2 does not represent halogen.
In the definitions, the hydrocarbon chains, such as alkyl, are in each case straight-chain or branched. Substituents may be identical or different.
Preferred substituents or preferred ranges of the radicals present in the formulae listed above and below are defined below.
R1 preferably represents hydrogen or halogen, or represents C1-6 alkyl which may be unsubstituted or substituted with halogen, hydroxy, C1-3 alkoxy, C1-3 alkylthio, C1-3 alkylcarbonyloxy, trifluoromethylcarbonyloxy or cyano, or represents C1-4 alkylsulfonyloxy or represents phenyl which may be unsubstituted or substituted with halogen, methyl, trifluoromethyl, methoxy, methylthio, methylsulfonyl, trifluoromethoxy, trifluoromethylthio, phenyl, phenoxy, cyano or nitro.
R2 preferably represents hydrogen or halogen or represents C1-6 alkyl which may be unsubstituted or substituted with C1-3 alkoxy or halogen, or represents C1-4 alkoxycarbonyl.
n preferably represents 0 or 2.
R1 particularly preferably represents hydrogen, fluoro, chloro or bromo, or represents C1-4 alkyl which may be unsubstituted or substituted with fluoro, chloro, bromo, hydroxy, C1-3 alkoxy, C1-3 alkoxy, C1-3 alkylthio, C1-3 alkylcarbonyloxy, trifluoromethylcarbonyloxy or cyano, or represents methylsulfonyloxy or ethylsulfonyloxy or represents phenyl which may be unsubstituted or substituted with fluoro, chloro, bromo, methyl, trifluoromethyl, methoxy, methylthio, methylsulfonyl, trifluoromethoxy, trifluoromethylthio, phenyl, phenoxy, cyano or nitro.
R2 particularly preferably represents hydrogen, fluoro, chloro or bromo or represents C1-4 alkyl which may be unsubstituted or substituted with C1-3 alkoxy or bromo or represents C1-3 alkoxycarbonyl.
n particularly preferably represents 0.
The novel compounds of the above-mentioned formula (I) are obtained, for example, by the following preparation processes a), b), c), d), e), f), g) or h).
Preparation Process a)
Compounds of the formula (I)
wherein
R1 represents hydrogen, represents alkyl which may be substituted with halogen, hydroxy, alkoxy, alkylthio, alkylcarbonyloxy, haloalkylcarbonyloxy or cyano or represents phenyl which may be substituted with halogen, alkyl, haloalkyl, alkoxy, alkylthio, alkylsulfonyl, haloalkoxy, haloalkylthio, phenyl, phenoxy, cyano or nitro,
R2 represents hydrogen or represents alkyl which may be substituted with alkoxy or halogen and
n represents 0
are obtained when compounds of the formula (II) 
wherein
R1a represents hydrogen, represents alkyl which may be substituted with halogen, hydroxy, alkoxy, alkylthio, alkylcarbonyloxy, haloalkylcarbonyloxy or cyano or represents phenyl which may be substituted with halogen, alkyl, haloalkyl, alkoxy, alkylthio, alkylsulfonyl, haloalkoxy, haloalkylthio, phenyl, phenoxy, cyano or nitro,
R2a represents hydrogen or represents alkyl which may be substituted with alkoxy or halogen and
n represents 0
are reacted with 4-bromo-1,1,2-trifluoro-1-butene in the presence of inert solvents and if appropriate, in the presence of an acid binder.
Preparation Process b)
Compounds of the formula (I)
wherein
R1 and R2 are as defined above, and
n represents 1 or 2
are obtained when compounds of the formula (Ia) 
wherein
R1 and R2 are as defined above
are oxidized in the presence of inert solvents.
Preparation Process c)
Compounds of the formula (I)
wherein
R1 represents hydrogen or haloalkyl,
R2 represents halogen, and
n represents 0
are obtained when compounds of the formula (Ib) 
wherein
R1b represents hydrogen or alkyl, and
R2b represents hydrogen
are reacted with a halogenating agent in the presence of inert solvents.
Preparation Process d)
Compounds of the formula (I)
wherein
R1 represents haloalkyl,
R2 represents hydrogen or haloalkyl and
n represents 0
are obtained when compounds of the formula (Ic) 
wherein
R1c represents alkyl, and
R2c represents hydrogen or alkyl,
are reacted with a halogenating agent in the presence of inert solvents.
Preparation Process e)
Compounds of the formula (I)
wherein
R1 represents halogen,
R2 represents hydrogen or alkyl and
n represents 0,
are obtained when compounds of the formula (III) 
wherein
R2d represents hydrogen or alkyl,
are reacted with a halogenating agent in the presence of inert solvents, and, if appropriate, in the presence of an organic base.
Preparation Process f)
Compounds of the formula (I)
wherein
R1 represents alkylsulfonyloxy,
R2 represents hydrogen or alkyl and
n represents 0
are obtained when compounds of the aforementioned formula (III) are reacted with compounds of the formula
R1dSO2Clxe2x80x83xe2x80x83(IV) 
wherein
R1d represents alkyl
in the presence of inert solvents, and if appropriate, in the presence of an inorganic or organic base.
Preparation Process g)
Compounds of the formula (I)
wherein
R1 represents alkyl,
R2 represents alkoxycarbonyl and
n represents 0
are obtained when compounds of the formula (IV) 
wherein
R1c is as defined above, and
R3 represents alkyl,
are reacted with thiourea and the products are then reacted with 4-bromo-1,1,2-trifluoro-1-butene in the presence of inert solvents.
Preparation Process h)
Compounds of the formula (I)
wherein
R1 represents hydrogen,
R2 represents alkoxyalkyl and
n represents 0
are obtained when compounds of the formula (Id) 
wherein
R1e represents hydrogen,
are reacted with compounds of the formula (VI)
R4xe2x80x94Brxe2x80x83xe2x80x83(VI) 
wherein
R4 represents alkoxyalkyl,
in the presence of inert solvents.
The compounds of the formula (I) of the present invention exhibit strong nematicidal activity and show good compatibility with various crops.
The compounds of the formula (I) according to the present invention surprisingly show a very outstanding nematicidal activity compared with the compounds described in the aforementioned literature which are similar to the compounds of the present invention.
In the present specification xe2x80x9chalogenxe2x80x9d represents fluoro, chloro, bromo or iodo, preferably represents fluoro, chloro or bromo, and particularly preferably represents chloro or bromo.
xe2x80x9cAlkylxe2x80x9d and each alkyl part of xe2x80x9calkoxyxe2x80x9d, xe2x80x9calkylthioxe2x80x9d, xe2x80x9calkylcarbonyloxyxe2x80x9d, xe2x80x9calkylsulfonyloxyxe2x80x9d and xe2x80x9calkoxycarbonylxe2x80x9d represents a straight-chain or branched-chain alkyl such as methyl, ethyl, n- or i-propyl, n-, i-, s- or -t-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, preferably represents methyl, ethyl, n- or i-propyl, n-, i-, s-, or t-butyl, n-pentyl or n-hexyl and particularly preferably represents methyl, ethyl, n- or i-propyl or n-, i-, s-, or t-butyl.
xe2x80x9cHaloalkylxe2x80x9d and each haloalkyl part of xe2x80x9chaloalkylcarbonyloxyxe2x80x9d, xe2x80x9chaloalkoxyxe2x80x9d and xe2x80x9chaloalkylthioxe2x80x9d represents alkyl substituted with at least one halogen, preferably represents C1-4 alkyl substituted with one or a plurality of halogen, and particularly preferably represents methyl, ethyl or n- or i-propyl substituted with one or a plurality of fluoro, chloro or bromo. xe2x80x9cHaloalkylxe2x80x9d preferably represents chloromethyl, bromomethyl or trifluoromethyl.
Very particular emphasis is given to the group of the compounds of the formula (I) wherein
R1 represents hydrogen, halogen, represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n-pentyl or n-hexyl, each of which may be substituted with halogen, hydroxy, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylcarbonyloxy, ethylcarbonyloxy, n- or i-propylcarbonyloxy, trifluoromethylcarbonyloxy or cyano, or represents methylsulfonyloxy, ethylsulfonyloxy, n- or i-propylsulfonyloxy, n-, i-, s- or t-butylsulfonyloxy or represents phenyl which may be substituted with halogen, methyl, trifluoromethyl, methoxy, methylthio, methylsulfonyl, trifluoromethoxy, trifluoromethylthio, phenyl, phenoxy, cyano or nitro,
R2 represents hydrogen, halogen, methyl, ethyl, n- or i-propyl, n-, i-, s-, or t-butyl, n-pentyl or n-hexyl each of which may be substituted with methoxy, ethoxy, n- or i-propoxy or halogen or represents methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl or n-, i-, s-, or t-butoxycarbonyl, and
n represents 0, 1 or 2.
However, if R1 represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n-pentyl or n-hexyl, R2 does not represent halogen.
Very particular preference is furthermore given to the group of compounds of the formula (I), wherein
R1 represents hydrogen, fluoro, chloro, bromo, represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, each of which may be substituted with fluoro, chloro, bromo, hydroxy, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, trifluoromethylcarbonyloxy or cyano, or represents methylsulfonyloxy or ethylsulfonyloxy, or represents phenyl which may be substituted with fluoro, chloro, bromo, methyl, trifluoromethyl, methoxy, methylthio, methylsulfonyl, trifluoromethoxy, trifluoromethylthio, phenyl, phenoxy, cyano or nitro,
R2 represents hydrogen, fluoro, chloro, bromo, represents methyl, ethyl, n- or i-propyl or n-, i-, s- or t-butyl each of which may be substituted with methoxy, ethoxy, n- or i-propoxy or bromo or represents methoxycarbonyl, ethoxycarbonyl or n- or i-propoxycarbonyl, and
n represents 0, 1 or 2.
However, if R1 represents methyl, ethyl, n- or i-propyl or n-, i-, s- or t-butyl, R2 does not represent fluoro, chloro or bromo.
The aforementioned preparation process a) can be represented by the following reaction scheme if, for example, 2-mercaptooxazole and 4-bromo-1,1,2-trifluoro-1-butene are used as starting materials. 
The aforementioned preparation process b) can be represented by the following reaction scheme, if, for example, 2-(3,4,4-trifluoro-3-butenylthio)oxazole is used as starting material and m-chloroperbenzoic acid is used as oxidizing agent. 
The aforementioned preparation process c) can be represented by the following reaction scheme, if, for example, 2-(3,4,4-trifluoro-3-butenylthio)oxazole is used as starting material and sulfuryl chloride is used as halogenating agent. 
The aforementioned preparation process d) can be represented by the following reaction scheme, if, for example, 4-methyl-2-(3,4,4-trifluoro-3-butenylthio)oxazole is used as starting material and N-chlorosuccinimide is used as halogenating agent. 
The aforementioned preparation process e) can be represented by the following reaction scheme, if, for example, 2-(3,4,4-trifluoro-3-butenylthio)oxazolidin-4-one is used as starting material and phosphorus oxychloride is used as halogenating agent. 
The aforementioned preparation process f) can be represented by the following reaction scheme, if, for example, 2-(3,4,4-trifluoro-3-butenylthio)oxazolidin-4-one and methanesulfonic chloride are used as starting materials. 
The aforementioned preparation process g) can be represented by the following reaction scheme, if, for example, 2-chloro-5-methoxycarbonyl-4-methyloxazole, thiourea and 4-bromo-1,1,2-trifluoro-1-butene are used as starting materials. 
The aforementioned preparation process h) can be represented by the following reaction scheme, if, for example, 2-(3,4,4-trifluoro-3-butenylthio)oxazole and bromomethyl methyl ether are used as starting materials: 
The compounds of the formula (II), used as starting material in the aforementioned preparation process a) include the known compounds described in the literature, for example in J. Org. Chem., (1988), 53 (5), 1113-1114; Collect. Czech. Chem. Commun. (1983), 48 (12), 3421-3425; Can. J. Chem., (1972), 50 (18), 3082-3083 etc.
As specific examples of the compounds of the formula (II) there can be mentioned,
2-mercaptooxazole,
2-mercapto-4-methyloxazole,
4-ethyl-2-mercaptooxazole,
2-mercapto-5-methyloxazole,
5-ethyl-2-mercaptooxazole,
2-mercapto-5-n-propyloxazole,
2-mercapto-4-n-propyloxazole,
2-mercapto-4-iso-propyloxazole,
2-mercapto-4-tert-butyloxazole,
2-mercapto-4,5-dimethyloxazole,
2-mercapto-4-phenyloxazole and so on.
4-Bromo-1,1,2-trifluoro-1-butene, used as starting material in the aforementioned preparation process a), is a known compound described in the document WO 86/07590.
The compounds of the formula (Ia), used as starting material in the aforementioned preparation process b), correspond to the compounds of formula (I) if n represents 0 and can be synthesized, for example, according to the aforementioned preparation process a).
As oxidizing agent used for the oxidation of the compounds of the above-mentioned formula (Ia) in the preparation process b) there can be mentioned those which are used usually in the field of organic chemistry, for example, hydrogen peroxide water, m-chloroperbenzoic acid, peracetic acid, perbenzoic acid, magnesium monoperoxyphthalate, potassium peroxymonosulfate and so on.
The compounds of the formula (Ib) and the formula (Ic), used as starting materials in the aforementioned preparation process c) and preparation d), respectively, are generally described by the formula (I) of the present invention, wherein n represents 0. They can be synthesized, for example, according to the aforementioned preparation process a).
As halogenating agent, which can be reacted with the compounds of the formula (Ib) and the formula (Ic) in the preparation process c) and preparation d), respectively, there can be mentioned those which are used usually in the field of organic chemistry, for example, sulfuryl chloride, N-chlorosuccinimide, N-bromosuccinimide, trichloroisocyanuric acid, potassium fluoride, chlorine gas, bromine, iodine and so on.
The compounds of the formula (III) used as starting materials in the aforementioned preparation process e) and preparation f) are novel compounds which were not described in the literature before. They can be prepared, for example, according to the following process i).
Preparation Process i)
Compounds of the formula (III) are obtained when compounds of the formula (VII) 
wherein
R2d is as defined before,
are reacted with 4-bromo-1,1,2-trifluoro-1-butene in the presence of an inert solvent, and, if appropriate, in the presence of an acid binder.
The compounds of the above-mentioned formula (VII) include known compounds and can be synthesized, for example, according to the process described in Ukrain. Khim. Zhur., 16, 545-551 (1950).
As specific examples of the compounds of the aforementioned formula (III) there can be mentioned, for example,
2-(3,4,4-trifluoro-3-butenylthio)oxazolidin-4-one,
5-methyl-2-(3,4,4-trifluoro-3-butenylthio)oxazolidin-4-one and so on.
As halogenating agents, which can be reacted with the compounds of the aforementioned formula (III) in the preparation process e) there can be mentioned phosphorus oxychloride, phosphorus oxybromide, phosphorus pentachloride and so on.
The compounds of the aforementioned formula (IV), which are needed in the preparation process f), are well known in the field of organic chemistry. Specific examples which can be mentioned are methanesulfonic chloride, ethanesulfonic chloride etc.
The compounds of the formula (V) used as starting materials in the aforementioned preparation process g), are known compounds and can be prepared, for example, according to the process described in document WO 95/24403.
Specific examples of the compounds of the aforementioned formula (V) which can be mentioned are 2-chloro-5-methoxycarbonyl-4-methyloxazole, 2-chloro-5-ethoxycarbonyl-4-methyloxazole etc.
The compounds of the formula (Id) used as starting materials in the preparation process h) are generally described by the formula (I) of the present invention and can be synthesized, for example, according to the aforementioned preparation process a). Further, the compounds of the formula (VI), which are needed in the preparation process h), are well known compounds in the field of organic chemistry. Specific examples which can be mentioned are bromomethyl methyl ether, bromomethyl ethyl ether etc.
The reaction of the preparation process a) can be conducted in the presence of an adequate diluent. Examples of the diluents which can be used here are aliphatic, alicyclic and aromatic hydrocarbons, such as hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene or xylene; ethers, such as, diethyl ether, methyl ethyl ether, di-isopropyl ether, dibutyl ether, propylene oxide, dioxane or tetrahydrofuran; ketones, such as acetone, methyl ethyl ketone or methyl isobutyl ketone; nitriles, such as acetonitrile, propionitrile or acrylonitrile; acid amides, such as, dimethylformamide, dimethylacetamide or N-methylpyrrolidone.
The reaction of the preparation process (a) can be conducted in the presence of an acid binder. Acid binders which can be used are, for example, hydroxides, carbonates and alcoholates etc. of alkali metals, tertiary amines, such as, triethylamine, diethylaniline, pyridine, 4-dimethylaminopyridine, 1,4-diazabicyclo[2,2,2]octane (DABCO) or 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU).
The reaction of the preparation process a) can be conducted in a substantially wide range of temperature. In general, the processes are carried out at temperatures between 0xc2x0 C. and 150xc2x0 C., preferably between 20xc2x0 C. and 100xc2x0 C. Although said reaction is generally carried out under normal pressure, it can be optionally carried out under elevated pressure or under reduced pressure.
When carrying out the preparation process a), the compounds of the corresponding formula (I) can be obtained by reacting, for example, 0.7-1.5 moles of 4-bromo-1,1,2-trifluoro-1-butene with 1 mole of the compounds of the formula (II) in a diluent, for example, acetonitrile in the presence of 1-1.3 moles of an acid binder, for example, potassium carbonate, under reflux by heating.
Among the compounds of the formula (I) of the present invention which can be prepared by the preparation process a), the compounds the formula (I) wherein R1 represents hydroxymethyl, alkoxymethyl, halogenomethyl, alkylcarbonyloxy, alkylthiomethyl or cyanomethyl, R2 represents hydrogen and n represents 0, can be also synthesized according to other processes described in Synthesis Examples 10-14 below.
The reaction of the preparation process b) can be carried out in the presence of an adequate diluent. Examples of the diluents which can be used are aliphatic, alicyclic and aromatic hydrocarbons which may be optionally chlorinated, such as, hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, ethylene chloride or chlorobenzene; ethers, such as, diethyl ether, methyl ethyl ether, di-isopropyl ether, dibutyl ether, propylene oxide, dioxane or tetrahydrofuran; alcohols, such as, methanol, ethanol, isopropanol, butanol or ethylene glycol; esters, such as, ethyl acetate or amyl acetate; acid amides, such as, dimethylformamide, dimethylacetamide or N-methylpyrrolidone; carboxylic acids, such as, formic acid or acetic acid.
The reaction of the preparation process b) can be conducted in a substantially wide range of temperatures. In general, the processes are carried out at temperatures between xe2x88x9220xc2x0 C. and 100xc2x0 C., preferably between 0xc2x0 C. and 80xc2x0 C. Although said reaction is generally carried out under normal pressure, it can be optionally carried out under elevated pressure or under reduced pressure.
When carrying out the preparation process b), the compounds of the corresponding formula (I) can be obtained by reacting, for example, 0.8-3 moles of m-chloroperbenzoic acid with 1 mole of the compounds of the formula (Ia) in a diluent, for example, methylene chloride, at room temperature.
The reaction of the preparation processes c) and d) can be carried out in the presence of an adequate diluent. Examples of the diluents which can be used are aliphatic, alicyclic and aromatic hydrocarbons which may be optionally chlorinated, such as, hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, ethylene chloride or chlorobenzene; ethers, such as, diethyl ether, methyl ethyl ether, di-isopropyl ether, dibutyl ether, propylene oxide, dioxane or tetrahydrofuran; acid amides, such as, dimethylformamide, dimethylacetamide or N-methylpyrrolidone; sulfones and sulfoxides, such as, dimethyl sulfoxide or sulfolane.
The reaction of the preparation processes c) and d) can be conducted in a substantially wide range of temperatures. In general, the processes are carried out at temperatures between xe2x88x9220xc2x0 C. and 200xc2x0 C., preferably between 0xc2x0 C. and 150xc2x0 C. Although said reaction is generally carried out under normal pressure, it can be optionally carried out under elevated pressure or under reduced pressure.
When carrying out the preparation processes c) and d), the compounds of the corresponding formula (I) can be obtained by reacting e.g. 1-4 moles of N-chlorosuccinimide with 1 mole of the compounds of the formula (Ib) in a diluent, such as, carbon tetrachloride, under reflux by heating.
The reaction of the preparation process e) can be carried out in the presence of an adequate diluent. Examples of the diluent which can be used are hydrocarbons including halogenated hydrocarbons, ethers, nitrites and acid amides according to the list of diluents mentioned in the aforementioned preparation process b).
The reaction of the preparation process (e) can be carried out in the presence of an organic base. Organic bases which can be used are, for example, triethylamine, 1,1,4,4-tetramethylethylenediamine (TMEDA), N,N-dimethylaniline or pyridine.
The reaction of the preparation process e) can be carried out in a substantially wide range of temperatures. In general, the processes are carried out at temperatures between 0xc2x0 C. and 200xc2x0 C., preferably between 20xc2x0 C. and 120xc2x0 C. Although said reaction is generally carried out under normal pressure, it can be optionally carried out under elevated pressure or under reduced pressure.
When carrying out the preparation process e), the compounds of the corresponding formula (I) can be obtained by reacting, for example, 1-5 moles of a halogenating agent to 1 mole of the compounds of the formula (III) in the presence of pyridine.
The reaction of the preparation process f) can be carried out in the presence of an adequate diluent. Examples of the diluents which can be used are the same diluents as mentioned in the aforementioned preparation process e) and, in addition, there can be mentioned alkylsulfonyl chlorides, for example, methanesulfonyl chloride, ethanesulfonyl chloride or isopropylsulfonyl chloride.
Further, the reaction of the preparation process (f) can be carried out in the presence of inorganic bases and organic bases. Organic bases which can be used are the same ones as exemplified in the aforementioned preparation process e). Inorganic bases which can be used are, for example, sodium carbonate or potassium carbonate.
The reaction of the preparation process f) can be carried out in a substantially wide range of temperature. In general, the processes are carried out at temperatures between xe2x88x9220xc2x0 C. and 150xc2x0 C., preferably between 0xc2x0 C. and 130xc2x0 C. Although said reaction is generally carried out under normal pressure, it can be optionally carried out under elevated pressure or under reduced pressure.
When carrying out the preparation process f), the compounds of the corresponding formula (I) can be obtained by reacting, for example, 1-3 moles of a compound of the formula (IV) to 1 mole of the compounds of the formula (III) with an organic base, for example triethylamine, in the presence of a diluent, for example tetrahydrofuran.
The reaction of the preparation process g) can be carried out in the presence of an adequate diluent. Diluents which can be used are the same diluents as mentioned in the aforementioned preparation process a) and, in addition, alcohols, for example, methanol, ethanol or isopropanol.
The reaction of the preparation process g) can be carried out in a substantially wide range of temperature. In general, the processes are carried out at temperatures between 0xc2x0 C. and 150xc2x0 C., preferably between 20xc2x0 C. and 120xc2x0 C. Although said reaction is generally carried out under normal pressure, it can be optionally carried out under elevated pressure or under reduced pressure.
When carrying out the preparation process g), the compounds of the corresponding formula (I) can be obtained by reacting, for example, 1-1.5 moles of thiourea to 1 mole of the compounds of the formula (V) in a diluent, for example, ethanol and then reacting with 1-1.5 moles of 4-bromo-1,1,2-trifluoro-1-butene.
The reaction of the preparation process h) can be carried out in the presence of an adequate diluent. Diluents which can be used are, for example, the ethers exemplified before.
The reaction of the preparation process h) can be carried out in a substantially wide range of temperature. In general, the processes are carried out at temperatures between 100xc2x0 C. and 150xc2x0 C., preferably between xe2x88x9278xc2x0 C. and 100xc2x0 C. Although said reaction is generally carried out under normal pressure, it can be optionally carried out under elevated pressure or under reduced pressure.
When carrying out the preparation process h), the compounds of the corresponding formula (I) can be obtained by reacting, for example, 1-1.5 moles of the compounds of the formula (VI) to 1 mole of the compound of the formula (Id) in a diluent, for example, diethyl ether, in the presence of n-butyl lithium.
The reaction of the preparation process i) can be carried out in the presence of an adequate diluent. Diluents which can be used are the same diluents as mentioned in the aforementioned preparation process a).
The reaction of the preparation process (i) can be carried out in the presence of the same acid binder as mentioned in the aforementioned preparation process a).
The reaction of the preparation process (i) can be carried out by applying the same reaction temperatures and pressures mentioned in the aforementioned preparation process a).
When carrying out the preparation process i), the compounds of the corresponding formula (III) can be obtained by reacting, for example, 0.7-1.5 moles of 4-bromo-1,1,2-trifluoro-1-butene to 1 mole of the compounds of the formula (VII) in a diluent, for example, tetrahydrofuran, in the presence of 1-1.3 moles of triethylamine.
The compounds of the formula (I) of the present invention show a strong ability to control nematodes. They can, therefore, be efficiently used as nematicidal agents.
Furthermore, the compounds of the formula (I) of the present invention show no phytotoxicity against crops and at the same time exhibit the ability to specifically control harmful nematodes.
Examples of nematodes against which the active compounds of the formula (I) of the present invention can be applied are, for example, Pratylenchus spp., Globodera rostochiensis Wollenweber, Heterodera spp., such as, Heterodera glycines Ichinohe, Meloidogyne spp., Aphelenchoides basseyi Christie, Bursaphelenchus Xylophilis, Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans etc. However, the nematodes which can be controlled by said compounds are not limited to the above list.
The active compounds of the present invention can also be used as mixtures with other active compounds, such as, insecticides, bactericides, miticides, fungicides etc. in the form of their commercially useful formulation or in the application form prepared from those formulations. Possible components for the mixtures are insecticides, for example organophosphorus agents, carbamate agents, carboxylate type chemicals, chlorinated hydrocarbon type chemicals or chloronicotinyl type chemicals, insecticidal substances produced by microbes.
Further, the active compounds of the present invention can also be used as mixtures with synergists in such formulations and application forms as can be mentioned as commercially useful. A synergist itself must not be active, but enhances the action of the active compound.
The content of the active compounds of the present invention in a commercially useful formulation or application form can be varied in a wide range. The application concentration of the active compounds of the formula (I) of the present invention can be in the range of generally 0.000001-100% by weight, preferably 0.00001-1% by weight.
The active compounds of the present invention can be converted into the customary formulations, such as, solutions, emulsions, wettable powders, water dispersible granules, suspensions, powders, foaming agents, pastes, granules, active compound-impregnated natural and synthetic substances, microcapsules, fumigants etc.
These formulations can be prepared according to per se known methods, for example by mixing the active compounds with extenders, namely liquid solvents, liquefied gas and/or solid diluents or carriers, and optionally with surfactants, namely emulsifiers and/or dispersants and/or foam formers. When water is used as extender, it is also possible to use, for example, organic solvents as auxiliary solvents.
Liquid diluents or carriers which can be used are, for example, aromatic hydrocarbons, such as, xylene, toluene or alkylnaphthalene, chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as, chlorobenzenes, ethylene chlorides or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, such as mineral oil fractions, alcohols, such as, butanol, glycols and their ethers or esters, ketones, such as, acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as, dimethylformamide or dimethyl sulphoxide, water and so on.
Liquefied gas diluents or carriers are liquefied substances which are gases at normal temperature and pressure. Examples are aerosol propellants such as butane, propane, nitrogen gas, carbon dioxide and halogenated hydrocarbons.
Solid diluents which can be used are, for example, ground natural minerals such as kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, ground synthetic minerals such as highly dispersed silicic acid, alumina or silicates and so on.
Solid carriers for granules which can be used are for, example, crushed and fractionated rocks, such as, calcite, marble, pumice, sepiolite or dolomite synthetic granules of inorganic and organic meals, particles of organic materials, such as, sawdust, coconut shells, maize cobs or tobacco stalks and so on.
Emulsifiers and/or foam-forming agents which can be used are, for example, nonionic and anionic emulsifiers, such as, polyoxyethylene fatty acid esters or polyoxyethylene fatty acid alcohol ethers, such as, alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates or arylsulphonates, albumin hydrolysis products and so on.
Dispersants include, for example, ligninsulphite waste liquor and methyl cellulose.
Tackifiers may also be used in formulations, such as, powders, granules or emulsions. Tackifiers which can be used are, for example, carboxymethyl cellulose, natural and synthetic polymers, such as, gum arabic, polyvinyl alcohol or polyvinyl acetate.
Colorants may also be used. Colorants which can be used are, for example, inorganic pigments such as iron oxide, titanium oxide or Prussian Blue, organic dyestuffs, such as, alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs, and further trace nutrients, such as, salts of metals such as iron, manganese, boron, copper, cobalt, molybdenum or zinc.
Said formulations generally comprise the aforementioned active components in a range of between 0.1-95% by weight, preferably between 0.5-90% by weight.
The preparation and use of the compounds of the present invention will be described more specifically in the following examples. However, the present invention should not be restricted to them in any way. xe2x80x9cPartsxe2x80x9d means xe2x80x9cparts by weightxe2x80x9d unless specified.